US4855215A - Photosetting polymer composition - Google Patents
Photosetting polymer composition Download PDFInfo
- Publication number
- US4855215A US4855215A US07/108,787 US10878787A US4855215A US 4855215 A US4855215 A US 4855215A US 10878787 A US10878787 A US 10878787A US 4855215 A US4855215 A US 4855215A
- Authority
- US
- United States
- Prior art keywords
- compound
- formula
- copolymer
- photosetting
- polymer composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 229920001577 copolymer Polymers 0.000 claims abstract description 68
- 229920005601 base polymer Polymers 0.000 claims abstract description 15
- -1 acrylate compound Chemical class 0.000 claims abstract description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 12
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical class CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 56
- 150000008065 acid anhydrides Chemical group 0.000 claims description 31
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 14
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical class NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 9
- 238000007142 ring opening reaction Methods 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
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- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 claims description 3
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- 229940059574 pentaerithrityl Drugs 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229940093475 2-ethoxyethanol Drugs 0.000 claims 4
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims 4
- JJBFVQSGPLGDNX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(=O)C(C)=C JJBFVQSGPLGDNX-UHFFFAOYSA-N 0.000 claims 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 claims 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims 2
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims 2
- TURITJIWSQEMDB-UHFFFAOYSA-N 2-methyl-n-[(2-methylprop-2-enoylamino)methyl]prop-2-enamide Chemical compound CC(=C)C(=O)NCNC(=O)C(C)=C TURITJIWSQEMDB-UHFFFAOYSA-N 0.000 claims 2
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 claims 2
- MQAWJNZATOEGJI-UHFFFAOYSA-N 4-(oxiran-2-yl)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCC1CO1 MQAWJNZATOEGJI-UHFFFAOYSA-N 0.000 claims 2
- WQZMWDXLSUFOEM-UHFFFAOYSA-N 4-(oxiran-2-yl)butyl prop-2-enoate Chemical compound C=CC(=O)OCCCCC1CO1 WQZMWDXLSUFOEM-UHFFFAOYSA-N 0.000 claims 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims 2
- ZCNCAQZNFJXUFA-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.OCC(CO)(CO)CO ZCNCAQZNFJXUFA-UHFFFAOYSA-N 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 1
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 abstract description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 abstract description 2
- 229910000679 solder Inorganic materials 0.000 description 21
- 239000000243 solution Substances 0.000 description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 230000004907 flux Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000018109 developmental process Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 206010034972 Photosensitivity reaction Diseases 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229960004050 aminobenzoic acid Drugs 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 230000036211 photosensitivity Effects 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 238000012719 thermal polymerization Methods 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
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- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
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- 230000007423 decrease Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
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- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 2
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
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- 239000000376 reactant Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
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- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- HNURKXXMYARGAY-UHFFFAOYSA-N 2,6-Di-tert-butyl-4-hydroxymethylphenol Chemical compound CC(C)(C)C1=CC(CO)=CC(C(C)(C)C)=C1O HNURKXXMYARGAY-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- KGQLBLGDIQNGSB-UHFFFAOYSA-N benzene-1,4-diol;methoxymethane Chemical compound COC.OC1=CC=C(O)C=C1 KGQLBLGDIQNGSB-UHFFFAOYSA-N 0.000 description 1
- LHMRXAIRPKSGDE-UHFFFAOYSA-N benzo[a]anthracene-7,12-dione Chemical compound C1=CC2=CC=CC=C2C2=C1C(=O)C1=CC=CC=C1C2=O LHMRXAIRPKSGDE-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- 229960001506 brilliant green Drugs 0.000 description 1
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- 238000011088 calibration curve Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- WUOBERCRSABHOT-UHFFFAOYSA-N diantimony Chemical compound [Sb]#[Sb] WUOBERCRSABHOT-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000007776 silk screen coating Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- JEVGKYBUANQAKG-UHFFFAOYSA-N victoria blue R Chemical compound [Cl-].C12=CC=CC=C2C(=[NH+]CC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 JEVGKYBUANQAKG-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
Definitions
- This invention relates to a process for preparing a denatured maleic anhydride-type copolymer having a controlled number of photosensitive groups, and to a photosetting polymer composition which comprises a base polymer comprising the denatured copolymer, a photopolymerizable monomer and a photopolymerization initiator.
- the photosetting polymer composition is advantageously used in industries relating to circuit-printable boards and circuit-printed boards as a solder resist solder mask), a marking ink, a solder leveler ink, a material for insulation of adjoining layers of a multilayer printed board, etc.
- thermosetting solder resists such as a resist of melamine resin type and a resist of epoxy resin type have been used. Recently a UV solder resist which is curable by ultra-violet rays has found use in consumer's goods. However, for use in industrial goods, the thermosetting solder resists such as the a resist of epoxy resin type is mainly used.
- thermosetting solder resist it is difficult to form a fine pattern because the pattern formation must be formed by a silkscreen printing process and the silk is apt to bend to lower presicion of positioning.
- a water soluble flux is more preferably used than a rosin type flux from the viewpoint of the simplicity of application.
- solder resists hardly have enough adhesion to the water soluble flux.
- an object of the present invention is to provide a photosetting composition having satisfactory heat-resistance, mechanical properties and chemical properties, by the use of which formation of a fine pattern can be done, covering with satisfactory positioning accuracy is accomplished, development with an aqueous alkaline solution can be performed, sufficient adhesion to a water soluble flux is attained.
- photosetting composition comprising:
- a base polymer comprising a denatured or base copolymer which is produced by reacting a copolymer of maleic anhydride and an unsaturated hydrocarbon compound, with a compound having the formula (I) and a compound having the formula (II): ##STR1## wherein R 1 is an alkylene group having 1-12 carbon atoms or an aromatic group and R 2 is a residue of a saturated compound having 1-12 carbon atoms, to open a portion of acid anhydride rings of the maleic anhydride units of the copolymer, heating the resulting copolymer to close a portion of units which have been formed by opening the rings with the compound of the formula (I) to form units having an imido structure, and reacting the resulting copolymer with a compound having the formula (III): ##STR2## wherein R 3 is an alkylene group having 1-12 carbon atoms or an aromatic group and R 4 is hydrogen or methyl, to introduce the (meth)acryloyl group of the compound of the
- the photosetting polymer composition of the present invention enables the formation of a fine-pattern and the covering with high precision by photolithography. Further, a film of the photosetting polymer composition can be developed easily with an aqueous alkaline solution, and shows adhesion resistant to provision of a water soluble flux thereon. Furthermore, the film shows high thermal resistance and satisfactory mechanical and chemical characteristics. The film is satisfactory in tacking. Accordingly, the photosetting polymer composition of the invention is advantageously used as insulating material of multilayer circuit-printed boards such as a solder resist, a marking ink and a solder leveler ink in circuit-board industries.
- the photosetting polymer composition of the invention can be obtained by incorporating another component in the reaction mixture without isolating the above-mentioned polymer after preparation of the base polymer. Therefore, the photosetting polymer composition of the invention is easily prepared.
- the denatured maleic anhydride-type copolymer used as the base polymer in the invention has the above-mentioned specific structure. If the denatured copolymer contains residual acid anhydride rings of more than 60% based on the number of the acid anhydride ring of the starting copolymer (in other words, the ratio of ring opening of acid anhydride rings caused by the compounds having the formulae (I), (II) and (III) is less than 40%), the solubility in an aqueous weak alkaline solution is made poor, so that the developability in the formation of a resist pattern worsens. If the ratio of the residual acid anhydride ring is too low, moisture resistance of the formed resist film is poor. Therefore, the denatured maleic anhydride copolymer preferably contains the residual acid anhydride ring in the range of 10-50%.
- the ratio of ring opening (opened-ring rate) of the above-mentioned acid anhydride group caused by the compounds having the formulae (I) and (II) preferably is in the range of 1:9 to 8:2. It is preferable that not less 80% of the ring-opened portions caused by the compound having the formula (I) are closed to form imido rings, from the viewpoint of thermal resistance and initial adhesion.
- the denatured maleic anhydride copolymer preferably has the ratio of the addition of (meth)acryloyl group of the compound (III) in the range of 2 to 50%.
- a proportion between the (meth)acryloyl group of the compound of the formula (III), which is attached to the carboxyl group formed by ring-opening of the acid anhydride ring by the compounds having the formulae (I) and (II), and the (meth)acryloyl group of the compound having the formula (III) that is reacted to the residual acid anhydride ring of the pre-denatured copolymer preferably is in the range of 2:1 to 10:1.
- the ratio of the residual acid anhydride ring in the denatured copolymer is calculated, by measuring IR spectra of the starting copolymer and the denatured copolymer. More specifically, the ratio of the residual (that is, unreacted) acid anhydride ring is calculated from change of the amount of peaks at 1770 cm -1 and 1850 cm -1 (peaks assigned to C ⁇ O of acid anhydride ring), referring to a peak at 650 cm -1 (peak assigned to the amido group of dimethylformamide).
- the ratio of addition of (meth)acryloyl group is calculated, by measuring NMR spectra of the reactant and the reaction product.
- the addition ratio is calculated from change of number of proton of doublebond of the hydroxyalkylene (meth)acrylate using a calibration curve which is prepared using as an internal reference octamethylcyclotetrasiloxane (OMCT).
- Examples of the unsaturated hydrocarbons to be copolymerized with maleic anhydride to form a copolymer which is the starting compound for the preparation of the above-mentioned denatured maleic anhydride copolymer include isobutylene, styrene, ⁇ -methylstyrene and p-vinylphenol. Particularly preferred is isobutylene.
- aminocarboxylic acid examples include glycine, ⁇ -alanine, and o-, m- and p-aminobenzoic acids.
- Examples of the compounds having the formula (II) include alcohols such as methanol and ethanol, and cellosolve derivatives such as ethylcellosolve and butylcellosolve.
- the cellosolve derivatives are particularly preferred.
- Examples of the compounds having the formula (III) include glycidyl (meth)acrylate and glycidylpropyl (meth)acrylate.
- the denatured maleic anhydride-type copolymer employable in the invention can be prepared by the following process.
- At least 80%, more preferably at least 90% of the constitutional units of the formula (V) are converted into a closed imido ring having the formula (VII): ##STR6## wherein R 1 , R 5 and R 6 having the same meanings as above.
- the denatured maleic anhydride copolymer employed in the composition of the invention preferably comprises a constituent unit of maleic anhydride including the constituent unit whose acid anhydride ring is opened by the compounds of the formulae (I), (II) and (III), and the constitutional unit of the unsaturated hydrocarbon within a ratio of about 1:1 to 1:10 and preferably has a number average molecular weight (Mn) in the range of about 1.0 ⁇ 10 4 to 2.0 ⁇ 10 6 .
- the denatured maleic anhydride copolymer employable in the composition of the invention is, for example, can be obtained by the following process.
- the maleic anhydride copolymer and compounds having the formulae (I) and (II) are reacted with each other in an organic solvent preferably at 70°-140° C., more preferably at 80°-100° C. for about 2-6 hours, and then after addition of an azeotropic solvent such as toluene or xylene, the reaction mixture is heated preferably at 80°-200° C., more preferably at 100°-150° C. for about 3 to 20 hours for performing a cyclizing-dehydrating reaction for the formation of an imido ring. By the reaction, the portion of rings opened by the compound of the formula (I) are converted into imido rings.
- the reaction product is heated in the presence of a compound of the formula (III) in an organic solvent preferably at 70°-140° C., more preferably at 80°-100° C. for about 2 to 5 hours to obtain the denatured copolymer.
- Examples of the photopolymerizable monomers which is one component of the photosetting polymer composition of the invention, include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, N,N'-methylene bis(meth)acrylamide, diethylaminoethyl (meth)acrylate, 1,3,5-triacryloylhexahydro-s-triazine, and tris(hydroxyethylacryloyl)isocyanurate.
- the photopolymerizable monomer is added in an amount of 5-500 weight parts, preferably 30-300 weight parts per 100 weight parts of the above-mentioned base polymer.
- the content of the monomer is less than 5 weight parts, the photo-sensitivity lowers and the cross-linking density decreases, whereby the developability, property of film formation and physical properties of the film (particularly, heat resistance and surface hardness) deteriorate.
- the content of the monomer is more than 500 weight parts, the cross-linking density extremely increases so that a formed film easily separates in a melted solder bath due to thermal shrinkage.
- photopolymerization initiators examples include Micheler's ketone, benzoin, bezoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, 4,4'-bis(diethylamino)benzophenone, acetophenone, benzophenone, thioxanthone, diethylthioxanthone, 1,5-acenaphthene, ethyl p-dimethylaminobenzoate and benzil.
- Micheler's ketone benzoin, bezoin methyl ether
- benzoin ethyl ether benzoin isopropyl ether
- 2-t-butylanthraquinone 1,2-benzo-9,10-anthraquinone
- 4,4'-bis(diethylamino)benzophenone
- the photopolymerization initiator is incorporated in the photosetting polymer composition of the invention in an amount of 1-50 weight parts, preferably 5-40 weight parts per 100 weight parts of the base polymer. In the case that the amount is less than 1 weight part, sufficient cross-linking is not attained by irradiation, and the photo-sensitivity lowers. In the case that the amount exceeds 50 weight parts, the photopolymerization initiator likely remains in the cured film to adversely effect the film property, while the photo-sensitivity does not rise any more.
- the photosetting polymer composition of the invention is soluble in organic solvents.
- the composition is used as a solution containing in an organic solvent the denatured copolymer, monomer and initiator in an amount of 30-90 weight %, preferably 50-90 weight %, namely, a photosetting polymer solution.
- the organic solvents include alcohols such as methyl alcohol, ethyl alcohol, butyl alcohol, n-propyl alcohol and isopropyl alcohol and cellosolve solvents such as ethylcellosolve and butylcellosolve.
- the photosetting polymer solution preferably has a rotation viscosity in the range of about 0.1 to 1,000 poise, more preferably 1-500 poise at the ordinary temperature.
- the photosetting polymer solution preferably contains an inorganic filler.
- the addition of the inorganic filler reduces the coefficient of linear expansion so that shrinkage by curing decreases, increases adhesion to a melted solder and the surface hardness, and further gives favorable influence upon printing characteristics.
- the inorganic fillers include mica, clay, talc, alumina white, diatomaceous earth, bentonite, wallastonite, quartz (SiO 2 ), aluminum hydroxide, calcium sulfate, barium sulfate, magnesium silicate, titanium dioxide, zinc oxide, silica alumina, and silicon nitride.
- the inorganic filler is preferably incorporated in an amount of 0-160 weight parts, more preferably 40-150 weight parts per 100 weight parts of the base polymer.
- the photosetting polymer solution may contain a thermal polymerization inhibitor, if desired.
- thermal polymerization inhibitors include hydroquinone, methylether hydroquinone, 2,6-di-t-butyl-4-methylphenol (BHT), benzoate, benzoquinone and 4-hydroxymethyl-2,6-di-t-butylphenol.
- the thermal polymerization inhibitor is preferably contained in an amount of 0.01-5 weight parts, more preferably 0.05-1 weight part per 100 weight parts of the base polymer.
- the photosetting polymer solution may contain, if desired, a dye or pigment such as phthalocyanine blue, phthalocyanine green, cyanine green, titanium white, titanium yellow, carbon black, chrome yellow, Hansa Yellow, Lake Red, methyl violet, brilliant green, and victoria blue, a thixotropy-increasing agent such as aerogil (available from Nippon Aerogil Co., Ltd.), an antifoaming agent such as dialkylpolysiloxane, both of which are effective to increase printability, and a fire-retardant such as diantimony pentoxide.
- a dye or pigment such as phthalocyanine blue, phthalocyanine green, cyanine green, titanium white, titanium yellow, carbon black, chrome yellow, Hansa Yellow, Lake Red, methyl violet, brilliant green, and victoria blue
- a thixotropy-increasing agent such as aerogil (available from Nippon Aerogil Co., Ltd.)
- the photosetting polymer composition can be employed in the form of the photosetting solution to form an insulative overcoat film, in the following manner.
- the photosetting polymer solution is coated on a substrate, and then is dried to evaporate the organic solvent.
- the coating on the substrate for example, can be done by curtain coating, roll coating, silk screen coating, dip coating, docter knife coating, etc.
- the coated film can be dried using hot air, far infrared rays, etc., preferably at a temperature of lower than 100° C., more preferably at a temperature of lower than 80° C.
- the drying procedure can be performed under normal or reduced pressure.
- a negative film is placed on the coated film, and is irradiated with rays emitted from, for example, a high pressure mercury lamp, a ultra-high pressure mercury lamp, a xenon lamp, a metal halide lamp, etc.
- the irradiated film is then developed by spraying a developing solvent or by dipping the film into a developing solution, and the unexposed part is washed off.
- a developing solvent such as aqueous sodium carbonate solution having a concentration of 1-5% may be used.
- the organic solvent listed for the preparation of the aforementioned photosetting polymer solution can be employed as the developing solution.
- heat treatment is performed, for example, for 30-60 minutes at 100°-150° C. using hot air or far infrared rays, or using irradiation with rays by means of three ultra-high pressure mercury lamps having 80-120 W/cm at a rate of 1-4 m/min, whereby an insulative overcoat film is produced.
- Isoban-04 available from kuraray Isoprene Chemical Co., Ltd., copolymer of maleic anhydride and isobutylene, namely, maleic anhydride copolymer
- p-aminobenzoic acid compound of the formula (I)
- butyl cellosolve compound of the formula (II)
- toluene azeotropic solvent
- the reaction product was then heated with glycidyl methacrylate (compound of the formula (III)) under the reaction conditions indicated in Table 1 to obtain a denatured copolymer.
- the ratio of the acid anhydride ring remaining in the denatured copolymer (residual ring ratio, determined from variation of peak strength of IR spectrum according to the method described hereinbefore), the ratio of addition of the methacryloyl group, and a ratio of imido group closed with the compound of the formula (I) (imidation ratio) are set forth in Table 1.
- Molar ratio means a molar ratio of p-aminobenzoic acid to the maleic anhydride unit of the copolymer before it was denatured.
- Photosetting polymer solutions having the undermentioned composition were prepared using the denatured maleic anhydride copolymers obtained in the abovementioned Production Examples 1-3 and Comparison Production Examples 1-3, for Examples 1-3 and Comparison Examples 1-3, respectively.
- a photoset film of the polymer composition having a thickness indicated in Table 2 was then formed in the undermentioned manner using the obtained solution.
- the obtained film was evaluated with respect to its luster, developability and other physical properties. The results are set forth in Table 2.
- Antifoaming agent 10 weight parts
- Thermalpolymerization inhibitor 1 weight part (Hydroquinone)
- the photosetting polymer solution is coated on a laminated plate of epoxidized glass-copper by screen printing.
- the coated plate is dried in an oven at 80° C. for 15 min. to remove the solvent.
- Exposure is performed at 500 mJ/cm 2 using a 2 KW ultra-high pressure mercury lamp (available from Oak Manufacturing Co., Ltd.
- the exposed plate is developed using aqueous 1% Na 2 CO 3 solution by a dipping process or a spraying process (2 Kg/cm 2 ). After the development is complete, the plate is washed.
- the plate is heated in an oven at 150° C. for 30 min., or the plate is irradiated by means of three 80 W/cm ultra-high pressure lamps at rate of 2 m/min.
- sensitivity On the overcoat film having been subjected to prebaking is placed a Kodak step tablet (gray scale) and thus combined plate is exposed at 1.5 J/cm 2 .
- a Quantity of radiation required for completely curing the film is calculated from the condition of the residual photoset film after the development. Thus obtained quantity of radiation is referred to as sensitivity.
- Pencil Hardness is determined according to JIS (Japanese Industrial Standard)-D-0202 8-10.
- Cross-cut adhesion test is done according to JIS-D-0202 8-12 after having dipped the plate in a melted solder bath (260° C.). A rosin type flux and a water soluble flux (Cl amount: 2.2%) are used.
- the plate is boiled for 2 hours and a cross-cut adhesion test is done according to JIS-D-0202 8-12.
Abstract
Description
TABLE 1 __________________________________________________________________________ Production Example Production Example For Comparison 1 2 3 1 2 3 __________________________________________________________________________ Reactants Isoban-04 20.0 20.0 20.0 20.0 20.0 20.0 p-Aminobenzoic Acid 8.9 3.6 14.2 17.8 8.9 -- Butylcellosolve 47.7 52.3 43.1 -- 52.3 55.3 Molar Ratio 0.5 0.2 0.8 1.0 0.5 0 Glycidyl Methacrylate 4.6 4.6 4.6 4.6 4.6 4.6 Reaction Conditions Acid Anhydride 100° C. 100° C. 100° C. 100° C. 100° C. 100° C. Ring Opening 3 hrs 3 hrs 3 hrs 3 hrs 4 hrs 4 hrs Imido Ring 140° C. 140° C. 140° C. 140° C. 140° C. 140° C. Closure 3 hrs 3 hrs 3 hrs 3 hrs 3 hrs 3 hrs Addition of 80° C. 80° C. 80° C. 80° C. 80° C. 80° C. Acrylate 3 hrs 3 hrs 3 hrs 3 hrs 3 hrs 3 hrs Residual Ring Ratio (%) 27 32 25 23 42 37 Methacryloyl Addition Ratio (%) 7.0 6.7 7.1 3.8 7.5 11.0 Imidation Ratio (%) Almost all imidated 32 0 __________________________________________________________________________
TABLE 2 ______________________________________ Example Comparison Example 1 2 3 1 2 3 ______________________________________ Film Thick- ness(μm) 10 10 10 10 10 10 Luster AA AA AA CC AA AA Developability AA AA BB BB AA CC Photosensitivity (mJ/cm.sup.2) less than 500 Resolution less than 75 Pencil Hardness 4H 4H 4H 4H 4H 4H Adhesion AA AA AA AA AA BB Moisture Resistance AA AA AA AA AA CC Heat Resistance to Solder (1) Rosin type I AA AA AA AA AA AA II AA AA AA AA AA AA III AA AA AA AA AA AA IV AA AA AA AA AA AA V AA AA AA AA AA AA (1) Water soluble type VI AA AA AA AA AA AA VII AA AA AA AA AA CC VIII AA AA AA AA BB CC IX AA AA AA AA CC CC ______________________________________
Claims (14)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61244944A JPH06828B2 (en) | 1986-10-15 | 1986-10-15 | Photocurable composition |
JP61-244944 | 1986-10-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
US4855215A true US4855215A (en) | 1989-08-08 |
Family
ID=17126284
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/108,787 Expired - Fee Related US4855215A (en) | 1986-10-15 | 1987-10-15 | Photosetting polymer composition |
Country Status (2)
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US (1) | US4855215A (en) |
JP (1) | JPH06828B2 (en) |
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US5130347A (en) * | 1987-12-30 | 1992-07-14 | Minnesota Mining And Manufacturing Company | Photocurable ionomer cement systems |
US5227413A (en) * | 1992-02-27 | 1993-07-13 | Minnesota Mining And Manufacturing Company | Cements from β-dicarbonyl polymers |
US5523383A (en) * | 1990-01-30 | 1996-06-04 | Nippon Petrochemicals Co., Ltd. | Photocurable resin composition for the preparation of a printed wiring board and process for the preparation of photocurable resin |
US5539064A (en) * | 1993-03-02 | 1996-07-23 | Goo Chemical Industries Co., Ltd. | Resist ink composition, printed circuit board produced by using the composition and process for producing the printed circuit board |
US5591562A (en) * | 1993-10-15 | 1997-01-07 | Sony Corporation | Water and acid developable photoresist composition exhibiting improved adhesion |
US5650263A (en) * | 1993-08-16 | 1997-07-22 | Fuji Photo Film Co., Ltd. | Photopolymerizable composition, color filter, and production of color filter |
US5723261A (en) * | 1989-11-30 | 1998-03-03 | Tamura Kaken Co., Ltd. | Photopolymerizable composition |
US5744282A (en) * | 1995-04-19 | 1998-04-28 | Hitachi Chemical Co., Ltd. | Photosensitive resin compositions and photosensitive element using the same |
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US20150247061A1 (en) * | 2012-09-19 | 2015-09-03 | Akzo Nobel Coatings International B.V. | Aqueous Coating Compositions Including The Reaction Product Of Maleic Anhydride With An Unsaturated Compound And An Amine |
US20170349679A1 (en) * | 2014-12-24 | 2017-12-07 | Manac Inc. | Novel bromine-containing polymers and methods for producing the same |
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JP2547883B2 (en) * | 1990-04-06 | 1996-10-23 | タムラ化研株式会社 | Photosensitive resin composition |
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Cited By (19)
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US5130347A (en) * | 1987-12-30 | 1992-07-14 | Minnesota Mining And Manufacturing Company | Photocurable ionomer cement systems |
US5925715A (en) * | 1987-12-30 | 1999-07-20 | Minnesota Mining And Manufacturing Company | Photocurable ionomer cement systems |
US5723261A (en) * | 1989-11-30 | 1998-03-03 | Tamura Kaken Co., Ltd. | Photopolymerizable composition |
US5523383A (en) * | 1990-01-30 | 1996-06-04 | Nippon Petrochemicals Co., Ltd. | Photocurable resin composition for the preparation of a printed wiring board and process for the preparation of photocurable resin |
US5378785A (en) * | 1992-02-27 | 1995-01-03 | Minnesota Mining And Manufacturing Company | Cements from β-dicarbonyl polymers |
US5227413A (en) * | 1992-02-27 | 1993-07-13 | Minnesota Mining And Manufacturing Company | Cements from β-dicarbonyl polymers |
US5512611A (en) * | 1992-02-27 | 1996-04-30 | Minnesota Mining And Manufacturing Company | Cements from βdicarbonyl polymers |
US5539064A (en) * | 1993-03-02 | 1996-07-23 | Goo Chemical Industries Co., Ltd. | Resist ink composition, printed circuit board produced by using the composition and process for producing the printed circuit board |
US5650263A (en) * | 1993-08-16 | 1997-07-22 | Fuji Photo Film Co., Ltd. | Photopolymerizable composition, color filter, and production of color filter |
US5591562A (en) * | 1993-10-15 | 1997-01-07 | Sony Corporation | Water and acid developable photoresist composition exhibiting improved adhesion |
US5744282A (en) * | 1995-04-19 | 1998-04-28 | Hitachi Chemical Co., Ltd. | Photosensitive resin compositions and photosensitive element using the same |
US6060216A (en) * | 1995-04-19 | 2000-05-09 | Hitachi Chemical Co., Ltd. | Photosensitive resin composition and photosensitive element using the same |
US6228560B1 (en) | 1995-04-19 | 2001-05-08 | Hitachi Chemical Company, Ltd. | Photosensitive resin composition and photosensitive element using the same |
US6555290B1 (en) * | 1995-04-19 | 2003-04-29 | Hitachi Chemical Co., Ltd. | Photosensitive resin composition and photosensitive element using the same |
US6184305B1 (en) | 1996-09-15 | 2001-02-06 | Clariant Finance (Bvi) Limited | Radiation absorbing polymer and synthesis thereof |
US20150247061A1 (en) * | 2012-09-19 | 2015-09-03 | Akzo Nobel Coatings International B.V. | Aqueous Coating Compositions Including The Reaction Product Of Maleic Anhydride With An Unsaturated Compound And An Amine |
US9469785B2 (en) * | 2012-09-19 | 2016-10-18 | Akzo Nobel Coatings International B.V. | Aqueous coating compositions including the reaction product of maleic anhydride with an unsaturated compound and an amine |
US20170349679A1 (en) * | 2014-12-24 | 2017-12-07 | Manac Inc. | Novel bromine-containing polymers and methods for producing the same |
US10442876B2 (en) * | 2014-12-24 | 2019-10-15 | Manac Inc. | Bromine-containing polymers and methods for producing the same |
Also Published As
Publication number | Publication date |
---|---|
JPH06828B2 (en) | 1994-01-05 |
JPS6397601A (en) | 1988-04-28 |
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